68

CHAPTER 4

SYNTHESIS OF -BELITE CEMENT

4.1 PREAMBLE

In this chapter, details of experimental investigations on the

synthesis of -belites ( -Ca2SiO4 or -C2S)by three different methods viz.
hydrothermal-calcination route, solid state reaction method and
mechanochemical method are presented. The materials such as LS/CLS and
SF/NS are used in this study towards the synthesis of belites. The
characteristic features of the synthesized belite are studied extensively in this
chapter. Moreover, the combination of various characterization tools such as
XRD, TG-DTA-DTG, FT-IR, SEM/TEM with EDX and BET analysis
leading to a determination of the phase transformations occurred during the
processing of the precursors and the formation of -belite by various methods.

Experimental investigations have also been carried out to

characterize the influence of synthesized belite (by hydrothermal method) on
the strength aspect (cube compressive strength) due to replacement of cement
by belite in various percentages viz 10%, 20% and 30%. The MD analysis
software, Materials Studio V 6.1 is used to represent the molecular structure
of all the three types of -belites and to evaluate the inter-atomic distances of
the bonds of Ca-Ca, Si-O and Ca-O.
 69

4.2 HYDROTHERMAL METHOD

Synthesis of -Ca2SiO4 is a three-step process and Figure 4.1

depicts the schematic diagram of the preparation of belite phase materials.
The first step is the homogenized mixing of CLS / amorphous SF mixtures in
a stoichiometric ratio of 2 (Ca/Si = 2.0) with water to solid (w/s) ratio of
10 for 12 hrs by using magnetic stirrer. Next step is the preparation of calcium
silicate hydrate (C-S-H) by hydrothermal method at 225-250°C with a
pressure of 15 to 17 bar for 4 hrs without using any chemical stabilizer or
activator. The resultant product is then dried for a day and kept in oven at
105°C for 2 hrs to remove the excess water.

A small quantity of this intermediate product is used for

characterization studies by using TG-DTA/DTG, SEM and FT-IR. The SEM
image of the intermediate product namely, calcium silicate hydrate (C-S-H) is
as shown in Figure 4.2, which indicates the dense cluster pattern of C-S-H
(Meisztericset al. 2010).

Figure 4.1 Schematic diagram of preparation of -belite phase

The results of simultaneous TG-DTA-DTG of this intermediate

product are as shown in Figure 4.3. Based on the TG-DTA-DTG results, the
firing temperature is established towards the synthesis of belite. It is observed
that there are three mass loss transitions in the TG curve viz. (i) mass loss
(16.64 %) of chemically bound water and C-S-H between the temperature
100 - 400°C, (ii) mass loss (7.39%) transition occurs between 400 - 800°C
 70

due to the decomposition of portlandite (CH- calcium hydroxide) and/or

residual calcite (CC-calcium carbonate) phases in this temperature range and
(iii) mass loss (5.82%) transition between 800-1100°C due to the formation
new phases in this temperature range.

Figure 4.2 SEM micrograph of C-S-H (intermediate product)

The residual mass at 1200°C is about 70.15% during the entire

heating process. As per TG-DTA-DTG results, it is observed that there are
four endothermic transitions of intermediate products. The first two
endothermic peaks at 119°C and 165°C are pertaining to the decomposition
contents of chemically bound water and C-S-H respectively (Meisztericset al.
2010 and Baltakys et al. 2007). The third endothermic peak at around 850°C
is due to the formation of wollastonite phase (Meisztericset al. 2010, Almeida
& Sichieri 2006, Puntharoda et al. 2013).

It is observed that the formation of mono calcium silicate, namely

wollastonite (CS, CaSiO3), which is an intermediate phase and a metamorphic
 71

reaction product of CLS and SF. The occurrence of final endothermic

transition at the temperature of 1025°C could be due to different polymorphic
phase into new materials, which indicates the formation of belite phase at this
temperature. Hence, the intermediate powder product is pelletized by using
the automatic press with 7-9 tones pressure. The homogenized pellets are then
subjected to calcination at elevated temperature between 850 and 1100°C for
2h soaking period in order to study the possible formation of belite
-dicalcium silicate, -Ca2SiO4). The heating rate is fixed at 10 C/min. Air
cooling method is used for cooling the final product at the rate of 10 C/min
till reaching the room temperature. Finally, the reacted pellets are crushed into
fine powder and preserved in airtight containers for further characterization
studies.

Figure 4.3 TG-DTA-DTG of intermediate product

The powder XRD of all the heated samples at different

temperatures viz. 850, 900, 1000 and 1100°C are shown in Figure 4.4. It is
observed that the peaks relevant to wollastonite is formed (PDF No. 00-002-
 72

0689) for the sample heated at 850°C as discussed earlier. At 900°C, other
than belite phases, prominent peaks of lime (CaO, PDF No. 04-002-6758),
tobermorite like C-S-H (PDF No. 04-011-0271) and considerable quantity of
cristobolite (SiO2, PDF No. 01-071-0261) are observed.

Figure 4.4 XRD patterns of belite at 850, 900, 1000 and 1100°C

The decomposition of wollastonite phases, formed at 850°C,

transformed into lime and cristobolite is observed at 900°C. At the calcination
temperature of 1000°C, the samples show the uniformity in the formation of
polycrystalline belite composites (Figure 4.4). Figure 4.5 shows explicitly the
results of whole-powder-pattern for observed profile intensities of belite
synthesized at 1000 C by XRD and semi-quantitative (S-Q) analysis by using
 73

TOPAS academic software and the results are presented in Table 4.1. It can
be observed from Table 4.1 that about 89.3 % of -belite is formed with some
traces of lime (1.27%), cristobolite (1.97%), tobermorite (1.71%) and -phase
of belite (5.94%). There is low temperature metastable phase, namely -phase
belonging to monoclinic structures (space groups P21/n) with lattice
parameters as given in Table 4.1.

Figure 4.5 Results of whole-powder-pattern for observed profile

intensities of belite synthesized at 1000 C and calculated
intensities (grey lines)

The other phase of belite, that is, -C2S ( -C2SiO4, orthorhombic,

P63/mmc) is also formed at this temperature. The XRD patterns (Figure 4.5)
do not present any tri-calcium silicate (C3S, Alite) peak, which confirms the
formation of belite clinker of this sample. The minimum quantity of free lime
 74

(CaO) testifies the optimum calcination temperature of 1000°C without

decomposition of calcium silicate phases during cooling.

Table 4.1 Refined crystal structure parameters of belite synthesized at

1000°C by hydrothermal-calcination method

S-Q Space Lattice parameter

Formula Product type
(wt %) group a (Å) b (Å) c (Å) () () ()
-C2S(B)* -Belite 89.3 P21/n 9.31 6.76 5.51 90 94.46 90
-C2S -Belite 5.93 P63/mmc 5.41 5.41 6.89 90 90 90
C-S-H Tobermorite 1.71 Imm2 5.61 3.71 22.56 90 90 90
CaO Lime 1.24 Fm-3m 4.82 4.82 4.82 90 90 90
SiO2 Cristobolite 1.83 P412121 5.01 5.01 7.07 90 90 90
* -C2S(B) - -C2S(Berliner)

The chemical composition of the synthesized belite is presented in

Table 4.2 and the lime saturation factor (LSF) is calculated from the oxide
compounds. The LSF is important, because it controls the quality of the
cement clinkers.

Table 4.2 Chemical composition of synthesized belite

Oxide MgO+
SiO2 Al2O3 Fe2O3 CaO SO3 Na2O K2O LOIa
(wt%) MnO
-belite 21.9 0.29 0.33 74.6 0.92 0.32 0.43 0.81 <1.0

a
LOI = Mass loss on ignition

The LSF is defined as follows (Hewlett 1998):

LSF = (4.1)
×% ×% ×%
 75

According to equation(4.1), the calculated LSF from the oxide

compositions is 1.201, whereas the residual (experimental) LSF (Table 4.1,
lime contents) is 1.24. Upon further heating to 1100°C, there is a considerable
reduction in the quantity of -belite, whereas alite phase starts forming, which
is not the focus of this study. From the above experimental studies, it can be
observed that -Belite is synthesized at 1000°C, which is relatively low
temperature compared to conventional synthesis of belite at the temperature
more than 1200°C. Due to high specific surface area of SF particles, which
have high reactivity, by inducing chemical activations during hydrothermal
reaction with CLS materials. Hence, the -belite obtained at 1000°C is used
for detailed characterization studies such as SEM with EDX, FT-IR and BET
analysis. Further, mechanical properties of the formed belite incorporated
cement pastes and mortars are conducted.

4.2.1 Characterization Studies on Formed -belite

4.2.1.1 SEM studies

Figure 4.6 shows the SEM micrograph with E-DAX spectrum of

the formed belite, which indicate the short regular needle like morphology of
belite structure and uniform distribution of belite can be observed. There is a
clear distinction between the micrographs of C-S-H (Figure 4.2) and the
present one, which illustrates the morphological changes due to the
occurrence of the stated thermal reactions. The quantitative elemental analysis
by energy dispersive (EDX) pattern of belite indicates that there is a notable
trace of carbon atoms (11.3%) due to the presence of unburnt carbon during
calcination of raw LS materials and the sample loading in the carbon strips
during SEM analysis (Figure 4.6).
 76

Figure 4.6 SEM micrograph with quantitative elemental analysis by E-

DAX of synthesized belite at 1000 C

4.2.1.2 FT-IR spectroscopic analysis

Figure 4.7 illustrates FT-IR spectra of hydrothermally synthesized

C-S-H and calcined C-S-H at temperature of 1000°C. The reaction
mechanism between lime and amorphous silica by hydrothermal treatment
leading to the formation of intermediate C-S-H at 240°C, which gives rise to
strong absorption band at 964 cm 1
(vibrations of[ ] groups), at
1 1
869 cm (asymmetric stretching vibration of Si–O–Si), at 715 cm
(symmetric stretching vibration of Si–O–Si) (Meiszterics et al. 2010), and at
1
451 cm (bending vibration of O–Si–O) (Chen et al. 2011). Belite phases
give the following characteristic absorption bands mainly in the range
400 -1200 cm-1; three maxima at 996 and 845 cm 1
(Si–O–Ca symmetric
stretching vibration modes), the band at 882 cm-1 indicates asymmetric
1
stretching vibrations of Si-O and a strong band at 512 cm (Si–O out-of-
plane bending mode), which is in good agreement with literature (Guerrero
et al. 2005, Garbev et al. 2014, Fernández-Carrasco et al. 2012, Mollah et al.
2000). Hence, the FT-IR study confirms the formation of belite at 1000°C.
 77

Figure 4.7 FI-IR spectra of C-S-H and synthesized belite

4.2.2 Compressive Strength Test

The experimental investigations have been carried out to

characterize the influence of synthesized belite on the strength aspect (cube
compressive strength in this case) due to replacement of cement by belite in
various percentages viz 10%, 20% and 30% (Figure 4.8). For determination of
appropriate water cement ratio, standard consistency test has been conducted
and water cement ratio of 0.4 is appropriately arrived at. For the compressive
strength determination of cement mortar, cube specimens of 50 mm size with
a mix ratio of 1:3:0.4 are used. The mix proportion of mortar cubes are
presented in Table 4.3.
 78

Table 4.3 Mix proportions for mortars

Cement Belite ( -C2S) a Sand Water Super-

Specimen
(kg m-3) -3
(kg m ) -3
(kg m ) (kg m-3) plasticizer b
Control 455 0 1364 181 0
B10 410 45 1364 181 0.2%
B20 364 91 1364 181 0.5%
B30 319 136 1364 181 0.8%
a b
As a weight replacement of cement; As a percent of cement alone

Other than control specimen, the mortars made with three different
replacement proportions of synthesized belite (B10, B20 and B30) are cast
and tested after 3, 7 and 28 days of curing. The results show that the
compressive strength is comparable with control mix on all the days of
curing. As the replacement percentage increases, there is a slight reduction in
strength in all the cases. In the case of B10, the percentage of strength loss for
3, 7 and 28 days compared to control mortars are 7%, 15% and 6%
respectively. For B20, the reduction percentages are 15%, 17% and 18%
respectively and for B30, the reduction percentages are 18%, 20% and 21%
respectively.

Hence, the replacement of 10% of synthesized belite is optimum as

far as the strength is concerned. But the general tendency for the belite cement
is to gain the strength at the later day only even after a year or two. Hence, it
can be concluded that the total reactive belite content in the cement
replacement system for B10 samples, gives equivalent strength of neat cement
mortar.
 79

Figure 4.8 Compressive strength of control and synthesized belite

incorporated cement mortars (B10, B20 and B30) at 3, 7 and
28 day of curing

4.3 SOLID STATE REACTION

Dried LS and NS are added in 2:1 molar stoichiometric ratio and

mixed homogeneously by using ball mill (Retsch P100) with Ball to Powder
Ratio (BPR) as 10 for 60 min at 400 rpm. The mechanism of inclusion of NS
is normally based on two ways, viz. either as filler materials in concrete or
imparting pozzolanic property with the surrounding compounds. The latter
case is utilized for this study towards synthesizing belite nanocomposites. The
mixed powder is then pelletized by using the automatic press with 7-9 tons of
pressure.
 80

The homogenized pellets are then subjected to solid state reaction

at elevated temperatures between 800 and 850°C. The reacted pellets are
crushed into fine powder and preserved in airtight containers for further
characterization studies.

4.3.1 Thermal Analysis of Precursors

The results of simultaneous thermal analysis (TG-MS) of ball

milled and homogenized lime sludge and nanosilica powders as precursors
(Figure 4.9) shows clearly the decomposition of LS between 550-700°C with
the typical ions associated with mass to charge (m/e) number of 44, which
indicates evolution of carbon dioxide (CO2) at peak temperature of 686°C.
Further, it is observed that CO2 evolution peaks takes place twice at
temperature of 745 and 816°C, which could be due to the formation different
polymorphic phase transitions of the precursors into new materials. It is also
found that there is a sharp exothermic peak at 817°C, which confirms the
formation of new phase in DTA graph. The residual mass at 1000°C is about
68% during the entire heating process.

4.3.2 Characterization of Intermediate and Final Products

According to equation (4.2) and as per TG-MS-DTA results, it is

observed that the formation of calcium silicate, namely wollasonite (CS,
CaSiO3), which is an intermediate phase and a metamorphic reaction product
of LS and NS, occurs at around 800°C. As such the powder XRD
(Figure 4.10) of the synthesized materials shows the relevant peaks of
wollasonite (PDF No.00-002-0689), which is formed at 800°C (labeled
lsns800 in Figure 4.10), but above 745°C, whereas the presence of
wollastonite is out of the scope for the present study.

CaCO3 (s) + SiO2(s) > 745 C CaSiO3 (s) + CO2 (g) (4.2)
 81

Figure 4.9 TG-MS-DTG graph of milled composites

The second exothermic peak found in TG-MS-DTA at 817°C

indicates the formation of a new phase in this region. Accordingly, the above
homogenized powders are heated further for the solid state reaction at 825°C
in order to study the possible formation of belite ( -dicalcium silicate,
-Ca2SiO4). As expected, the belite phase is formed at 825°C by the
subsequent reactions between formed wollastonite, residual LS and NS. The
air-cooling rate is fixed at 20°C/min till reaching the room temperature.

From the XRD spectrum (labeled lsns825 in Figure 4.10), it is

confirmed that the formation of -dicalcium silicate (PDF No.00-033-0302)
takes place at the reaction temperature of 825°C. In this study, it is further
noted that there are no peaks pertaining to the precursors as well as
intermediate product, i.e LS, NS and wollastonite etc., except portlandite
 82

(Ca(OH)2) traces at the sintering temperature of 825°C. This clearly shows the
uniformity in the preparation of polycrystalline belite nanocomposites.

Figure 4.10 XRD patterns of milled nano composites at different

temperature

Occurrence of traces of portlandite is due to the absorption of

moisture by CaO, which is formed during the decomposition of LS at elevated
temperature from the atmosphere. Moreover, the crystal structure of
synthesized belite is stable up to 850°C (labeled lsns850 in Figure 4.10),
which is confirmed through the XRD, whereas notable change appeared in the
phase when heated beyond 850°C. The crystallite size of the belite
nanocomposites is calculated by using the Scherrer's formula (equation 4.3):

d = 0.89 / cos2 (4.3)

 83

where d is crystallite size, is the wavelength of X-Ray (1.54056 Å), is full

width at half maximum (FWHM) of the respective intensity peaks and 2 is
the diffraction angle at high intensity peak. The average crystallite size of the
synthesized belite is calculated as 25 nm and the observed value is 27 nm.
The broadening of diffraction peaks indicates the amorphization under high
temperature, that is, above 800°C.

Figure 4.11 Results of whole-powder-pattern fitting for observed profile

intensities of belite synthesized at 825 C and calculated
intensities (grey lines)

Hence, results show that the optimum synthetic temperature to form

belite is 825°C. In addition, the present work reveals that the thermal energy
consumed during reaction is reduced significantly by about 28% of the
reported (Kurdowski et al. 1997) energy of around 1350 kJ/kg for the
conventional production of belite. Further, the refined crystal structure
parameters of the powder particles synthesized at 825°C estimated by the
Rietveld analysis (Semi-Quantitative) using TOPAS academic software are
 84

shown in the Table 4.4. Figure 4.11 shows the Rietveld refinement for belite
synthesized at 825°C.

There is low temperature metastable phase, namely the -phase and

the structures belong to monoclinic space groups P21/n (Jost et al. 1977) and
P21/c (Mumme et al. 1995 and Toraya & Yamazaki 2002) with lattice
parameters as given in Table 4.4. The other phase of belite, that is, 'L-C2S
(orthorhombic, Pnma) is also formed at this temperature.

Table 4.4 Refined crystal structure parameters of belite synthesized at

825°C by solid state reaction method

Lattice Constants Cell

S-
Compounds Space Group Volume
a (Å) b (Å) c (Å) () () () Q(%)
(Å^3)
'L-C2S 6.890 5.621 9.536 90 90 90 Pnma (62)$ 1.40 369.38
#
-C2S(J) 5.332 6.602 9.184 90 94.21 90 P21/n (14) 48.71 323.19
#
-C2S(M) 9.128 6.875 10.227 90 148.54 90 P21/c (14) 45.26 334.93
@
Portlandite 3.604 3.604 4.931 90 90 90 P-3m1(164) 4.63 55.46

$
Orthorhombic # Monoclinic and @ Hexagonal

-C2S(J) - -C2S(Jost) and -C2S(M) - -C2S(Mumme)

The functional group analysis by FTIR for materials synthesized at

800 °C (Figure 4.12) clearly indicate the broad wollastonite band with
characteristic peaks at ~ 847, 902, 1018 and 1084 cm-1 are due to the
symmetric stretching vibrations of Si-O-Ca and Si-O-Si bonds as predicted by
Meiszterics et al.(2010).

Figure 4.12 exhibits the belite synthesized at 825 and 850°C, with
significant bands appeared in the frequency range between 845-1010 cm-1
with characteristic peaks at 845, 922 and 1010 cm-1 due to stretching
vibrations of Si-O-Ca and Si-O-Si of silicate bands and the band at 520 cm-1
 85

also appears due to strong Si-O out-of-plane bending vibration of silicate and
these results are in good agreement with those in literature (Fernández-
Carrasco et al. 2012, Mollah et al. 2000).

Figure 4.12 FT-IR spectra of solid state reaction products

Further it is noted that the peaks at the frequencies between 643 and
682 cm-1 in Figure 4.12 (for 800°C), are associated to the characteristic peaks
of amorphous SiO2 in the wollastonite form, which are disappearing for the
subsequent heating towards the belite synthesis. Hence, FT-IR study confirms
the formation of belite phase from wollastonite phase at low temperature.

Hence, from the above experimental work, it is possible to

synthesize belite by means of thermal process of mechanically activated raw
materials such as LS and NS at relatively low temperature compared to
conventional belite synthesis at the temperature more than 1200°C. The above
 86

result could be possible because of nanosilica particles, which have high

reactivity due to its specific surface area, tendency to bond quickly with
surrounding materials, and to induce chemical activations during solid state
reaction with LS materials. Further, this is a new way of inducing phase
transformations in starting oxide powders, whose particles have dissimilar
sizes by using concurrent mechanical activation and high temperature solid
state reaction. In this case, LS in the micrometer scale and silica in nano
scale.

The typical morphology of the synthesized particles at 800°C and

825°C are studied by using SEM and are shown in Figure 4.13a & b. There is
a clear distinction between the micrographs, which illustrate the
morphological changes due to the occurrence of the stated reactions. The
regular spheroid like morphology with narrow size distribution of belite
structure with the particle width of 50-100 nm can be observed in Figure
4.13b. This can also be clearly observed in TEM image of the belite sample
synthesized at 825°C as shown in Figure 4.14a.

Table 4.5 EDAX analyses of belite synthesized at 825°C

Element Mass (%) Atomic(%)

C 7.46 17.11
O 14.70 25.30
Na 0.67 0.81
Si 18.78 18.41
Ca 51.49 35.37
Cu 6.86 2.97
 87

a b

Figure 4.13 SEM micrographs of solid-state reaction products, a.800°C

b.825°C

The energy dispersive X-Ray pattern is shown in Figure 4.14b.

There are notable traces of copper and carbon elements in EDAX pattern. The
former is due to the loading of sample in the copper grids, whereas later is
unburnt carbon deposit due to decomposition of LS materials. Table 4.5
shows the elemental data analyzed of the sample synthesized at 825°C. In the
case of higher temperature beyond 850°C, the occurrence of agglomeration of
belite into some other phases is observed.
 88

Figure 4.14(a) TEM image of solid-state reaction of belite at 825°C

Figure 4.14(b) Acquired E-DAX data of synthesized belite at 825ºC

 89

4.4 MECHANOCHEMICAL METHOD

Mechanochemically stimulated solid state reactions (dry process)

have become environmentally friendly than the wet processes.
Mechanochemical changes during high-energy ball milling of precursors and
subsequent heating of mechanosynthesized products yield target products
with less temperature compared to non-milled starting mixtures. An attempt is
made to synthesis belite by using calcined lime sludge (CLS) with highly
reactive nanosilica (NS) by mechanochemical method. The starting raw
materials, CLS and NS, are mixed in a stoichiometric ratio of 2. The raw
materials are ball milled in 500 ml agate vial and the milling experiments are
designed according to Table 4.6.

Separate samples are prepared by varying the milling parameters

and the effects of milling parameters on the formation of different
polymorphs of belite, (di-calcium silicate, C2S), which are monitored by
comparing XRD patterns with its respective standard ICDD PDF 4+ patterns.
In order to obtain -phase belite by mechanical activation of CLS and NS in
air atmosphere, milling is carried out in a planetary mill at various speed such
as 200, 300 & 400 rpm with time of mechanical activation as 60, 120, 180 and
240 minutes with constant ball-to-powder ratio (BPR) of 10:1 throughout all
the experiments. The formation of belite is observed by XRD analysis and the
semi-quantitative analysis results are presented in Table 4.6. Figures 4.15 (a),
(b) & (c) show the XRD patterns that are mechanically activated for various
milling parameters as stated above.

Certain amount of various forms of belite peaks can be found in the

XRD patterns. Since the milling is performed in an air atmosphere, in addition
to belite forms, the presence of calcite (calcium carbonate, CaCO3 : PDF No.
00-005-0586), portlandite (calcium hydroxide, Ca(OH)2 : PDF No. 00-004-
0733 and lime (calcium oxide, CaO : PDF No. 00-048-1467) are more
 90

evident. The moisture contents in the atmosphere influence the formation of

portlandite and calcite. These observations indicate the formation of small
amount of belite with shorter time of mechanical activation is not enough to
obtain more quantity of homogeneous belite. Hence, the milling duration and
speed are increased further to get the optimum value of milling parameters.
As such, the milling duration of 180 minutes and speed of 400 rpm are found
to be optimized values to get maximum quantity of -belite (PDF No.00-033-
0302) of about 70%. This is achieved because of the influence of nano SiO2
particles with higher surface area leading to high reactivity inducing chemical
reactions during milling with CLS materials. Moreover, the mechanical
activations are influenced by the ratio of the angular velocity of the planetary
balls and their kinetic energy transfer to the powders from the balls and wall
of the milling vial. It is furthermore, a way of inducing phase transformations
in starting powders, whose particles have dissimilar sizes.

In the present study, CLS is in micrometer scale, whereas the silica

is in nano-scale. In the case of planetary ball milling, the powders are cold
welded and fractured during mechanical alloying and the polymorphic phase
transformations of compounds occurred due to chemical transformation.
Therefore, by controlling the components at the microstructure level, the
desired physical and chemical properties can be achieved. It is further noticed
in the optimized case that the portlandite quantity is reduced to 2%, whereas
the calcite level is increased to 7.76%. It is necessary to emphasize here that
the presence of calcite, portlandite and lime even after prolonged milling is
clearly noticed, that is, extended milling beyond 180 min. Moreover,
prolonged milling is also directed to the formation of higher amount -form
of belite phase of around 68% (Table 4.6), whereas the -form of belite
reduced considerably to 7.46%. The BET surface area of milled product is
found as 21.96 m²/g. The morphology of formed belite powder after
mechanical activation as observed by SEM and TEM are shown in
Figures 4.16(a) and (b), which indicate the belite powder of varying sizes.
 91

Table 4.6 Semi-quantitative analysis of mechanical activation of CLS

and NS (BPR: 10)

Semi-quantitative composition (%) of compounds formed during milling

Speed, Milling
rpm ' L- 'H- -C2S -C2S Port-
duration -C2S -C2S Lime Calcite Quartz
C2S C2S (J) (M) landite
(min)
60 17.37 - - 18.61 7.73 7.14 30.39 17.46 - 1.30
120 15.35 - - 18.07 11.61 9.08 22.61 22.59 - 0.69
180 14.14 - - 23.03 16.79 10.77 13.84 20.87 - 0.56
200
0.21
240 11.80 - - 24.14 32.51 9.82 0.06 15.53 4.92

60 22.01 - 1.78 1.87 30.07 10.86 4.60 28.78 0.04 -

120 9.98 1.34 - 25.31 33.50 10.58 - 13.55 5.74 -
180 15.31 - - 31.59 27.43 12.00 - 6.49 7.17 -
300
2.28
240 10.87 27.17 - 34.49 10.79 10.79 - 5.69 8.62

60 23.92 - 12.06 7.34 18.40 2.57 25.09 10.54 0.06 -

120 6.57 - - 49.04 - 7.57 11.27 19.58 5.96 0.02
400 180 8.78 - - 38.74 32.69 8.51 1.50 2.01 7.76 -
240 16.51 16.75 44.64 - 7.46 4.25 - 1.90 5.78 2.72
-C2S(J) - -C2S(Jost) and -C2S(M) - -C2S(Mumme)

Figure 4.15 (Continued)

 92

Figure 4.15 XRD patterns at milling parameter of (a) 200 rpm, (b) 300
rpm and (c) 400 rpm for various times

Figure 4.16 (a) SEM image and (b) TEM micrograph of milled product

Thermal analysis, TG-DTA, of milled product (400 rpm and 180

min alone) helps to establish the influence of mechanical activation on solid
 93

state reaction and phase transition occurrence. Figure 4.17 shows the
TG-DTA pattern of the milled product. There is an endothermic peak in the
range between 400 and 450°C, which indicate the decomposition of
portlandite. Other event of exothermic hump observed at around 800 - 825°C
could be pertaining to solid state reaction between precursor oxides and phase
transition.

Accordingly, the above mechanically activated powders are heated

further for the solid state reaction at 825°C in order to get more of belite in -
phase. As expected, more quantity of -phase belite is formed at 825°C by
the subsequent reactions between residual CLS, calcite and NS. The air-
cooling rate is fixed at 20°C /min till reaching the room temperature. It is
confirmed by the XRD spectrum that the additional formation of -dicalcium
silicate (PDF No.00-033-0302) takes place at the reaction temperature of
825°C. Further the refined crystal structure parameters of the powder particles
synthesized at 825°C is estimated by the Rietveld analysis (Semi-
Quantitative) by using TOPAS academic software and are shown in Table 4.7
and Figure 4.18. It is found that there is a traceable quantity of portlandite
(2.74 %) and lime even after sintering.

About 4.19% of -phase of belite is also observed. The crystal

structure with lattice parameters of the products is provided in Table 4.7.
Hence, it is possible to synthesis -phase belite by mechanochemical method,
that is, mechanical activation followed be high temperature solid state
reaction, upto 93%. However, there is a considerable reduction of BET
surface area to 8.74 m²/g, which can be attributed to reduction in pore
diameter and amorphization upon sintering.
 94

Figure 4.17 TG-DTA graph of milled product

Figure 4.18 Results of whole-powder-pattern fitting for observed profile

intensities of belite synthesized at 825°C and calculated
intensities (grey lines)
 95

Table 4.7 Refined crystal structure parameters of belite synthesized at

825°C by mechanochemical method

Lattice Constants Cell

S-Q
Compounds Space Group Volume
Wt%
a (Å) b (Å) c (Å) () () () (Å^3)

P63/mmc
-C2S 5.40 5.407 6.959 90 90 90 4.19 176.26
(194)

-C2S(J) $ 5.30 6.602 9.026 90 94.21 90 P21/n (14) 49.1 315.94

-C2S(M) # 9.16 6.623 10.38 90 148.5 90 P21/c (14) 43.9 326.63

Portlandite 3.604 3.604 4.931 90 90 90 P-3m1(164) 2.74 55.01

Lime 4.75 4.759 4.759 90 90 90 Fm-3m (225) 0.03 107.79

$
-C2S(J) - -C2S(Jost) and # -C2S(M) - -C2S(Mumme)

The morphology of formed belite powder after mechanical

activation and sintering at 825°C are studied by SEM and TEM. Figure
4.19(a) indicates SEM image of belite powder consisting agglomerates and
TEM image shows the size of the particle in the range of 100-200 nm
(Figure 4.19(b)).

FT-IR system is used for this study to find the characteristics

absorption and vibration frequencies of the prepared belite samples. The IR
spectra of mechanically activated and thermally treated belite powders are as
shown in Figure 4.20. The FT-IR spectrum shows that the characteristic bands
appeared in the range of 400 - 1200 cm-1 significantly.

There is broad band in the wave number of around 952 cm-1 of the
milled product, which is spilt into bands at 845, 943 and 1084 cm-1 in the
sintered product due to the symmetric stretching vibrations of Si-O-Ca and Si-
O-Si bonds. The band at 520 cm-1 also appears due to strong Si-O out-of-
plane bending vibration of silicate. Moreover, the broad stretching vibration at
 96

around 3410 cm-1 is commonly attributed to O-H bond and the bands
associated with lime (2920, 1481 cm-1) appeared in the sintered product
spectrum.

Figure 4.19 (a) SEM image and (b) TEM image of milled sintered
product at 825°C

The peak at 2350 cm-1 due to carbon dioxide shows its presence in
the milled product, whereas the same has disappeared in the sintered product.
This result has already been discussed in the EDAX analysis. The absorption
band at 3640 cm-1 is due to the O-H bond, and its intensity reduces
considerably in the sintered product spectrum (Figure 4.20).
 97

Figure 4.20 FT-IR spectrum of milled (400-180) and sintered (825°C)

products

4.5 CRITICAL ANALYSIS OF ALL THE METHODS OF

SYNTHESIS OF BELITE

The highly reactive -belite is obtained with relatively high surface

area (4.073 m2 g-1) through hydrothermal assisted calcination reaction at
1000ºC when industrial by-products such as CLS and SF, are used as the
starting materials. As high as 89% of pure -belite with LSF of 1.21% is
synthesized without the use of any chemical stabilizers, this leads to potential
manufacture of low-temperature cement or OPC with low C3S, alite contents.

Because of early heat of hydration occurrence, the early setting

cement can be synthesized by using this kind of belite, which will be useful
for certain applications such as mass concreting in bridges, dams etc in order
 98

to reduce the thermal cracking due to the high heat liberations. However,
marginal reduction in compressive strength is observed in the mortars after
replacing cement with synthesized belites.

In the solid state reaction method, the laboratory experimental work

demonstrated the thermal analysis of mechanically activated raw materials
such as LS and NS aiming towards the synthesis of belite phase clinker. The
mechanothermal process influences the reaction kinetics of nano and micro
scaled materials, which reduces the sintering temperature towards the
synthesis of belite. It is observed that the thermal process towards the
formation of belite of mechanically activated dissimilar sized precursors
reduce the sintering temperature of the reaction significantly and belite is
obtained without the use of any chemical stabilizers and calcination
processing of LS. The BET specific surface area of belite clinker prepared in
this method is 8.173 m2 g-1 by using LS and NS at relatively low temperature
of 825°C. It is noticed that with further increase in the synthetic temperature,
there is a reduction in the specific surface area. The final product showed that
the spheroid crystallites in the range of 50-100 nm may lead to higher
hydraulic activity.

-C2S in OPC is slow in reaction nature during hydration and

depending upon the particle size of the reactive components, it is possible to
enhance its reaction kinetics. The influence of NS in the formation highly
reactive -phase belite ( -dicalcium silicate) with CLS materials by
mechanochemical method is studied. It is observed that -phase belite powder
has BET surface area of 21.96 m²/g after 180 min of milling with a optimum
speed of 400 rpm. With the formation of belite phase besides small amount of
calcite and portlandite, it is possible to trigger the solid state reaction
occurrence during intensive milling. The resulting belite after mechanically
activated solid state reaction exhibited the particle size in the range of 100-
 99

200 nm with a reduction in BET specific surface area to 8.74 m²/g. But after
sintering, the monoclinic structure of belite, that is -phase belite, is obtained,
which are most preferable in construction industry. Due to their ultrafine size,
the expected reactivity would be very high and it could improve the
mechanical properties for the repair and reinforcement for retrofitting or
restoration of heritage buildings, masonry structures, etc as grouting
materials.

Over all, the energy consumption for the preparation of -belites of

the three methods is less and the synthetic temperature is much less than the
conventional temperature of about 1200°C. In addition, the present work
reveals that the thermal energy consumed during reaction is reduced in the
range between 1010 -1140 kJ kg-1 (around 18 - 28 %) of the reported energy
of around 1,350 kJ.kg-1 for the production of conventional belite
(Kurdowskiet al. 1997). The characterization studies of the three types of
synthesized belites are conducted by means of XRD and Fourier transform -
infra red spectroscopy (FT-IR) analysis in order to study their molecular
structures and their atomic interactions in the unit cell and the vibrational
spectroscopic studies of these molecular structures. Among the three methods
of synthesis, the last two namely solid state reaction and mechanochemical
methods provide equal quantity of belite cement. Moreover, in these methods
LS/CLS and NS are used as precursors and the required calcination
temperature is 825°C.

4.5.1 XRD Analysis

From XRD analysis, all the three forms of -belites with lattice
parameters in the primitive unit cells and their space group are presented in
Table 4.8. By using the atomic coordinates and unit cell parameters, the
molecular structures of the individual belites are identified as monoclinic
crystal system with space group of either P21/n or P21/c.
 100

For the refined crystal structure parameters of the synthesized

belites from solid state reaction by using LS/NS, it is found from the XRD
spectrum that the percentage amount of -belite powder particles synthesized
at 825°C in this case is 93.98%. Moreover, two kinds of -belites are formed,
where the first one is -C2S (Jost) (Jost et al. 1977) with a quantity of 48.71%
and the second one is labeled as -C2S (Mumme)(Mumme et al. 1995), which
amounts to 45.26%. Similarly, -C2S (Berliner) (Berliner et al. 1997) is
synthesized by using CLS and SF with a maximum quantity of 89.3% by
hydrothermal-calcination route. From the XRD analysis, for all the three
forms of -belites, their atomic coordinates in the primitive unit cells are
given in Tables 4.8 and 4.9.

Table 4.8 Refined crystal structure parameters of synthesized -belites

by three methods

Lattice Constants Cell

Space
Samples S-Q (%) Volume
a (Å) b (Å) c (Å) () () () Group
(Å^3)

Solid state reaction method

-C2S[Jost] 5.332 6.602 9.184 90 94.21 90 P21/n 48.71 323.19

-C2S[Mumme] 9.128 6.875 10.227 90 148.5 90 P21/c 45.26 334.93

Mechanochemical method

-C2S[Jost] 5.332 6.602 9.184 90 94.21 90 P21/n 49.1 315.94

-C2S[Mumme] 9.128 6.875 10.227 90 148.5 90 P21/c 43.9 326.63
Hydrothermal method

-C2S [Berliner] 5.51 6.76 9.31 90 94.46 90 P21/n 89.23 346.21

By using the atomic coordinates and unit cell parameters, the

molecular structures of the individual belites are simulated by using molecular
dynamic (MD) analysis in order to find the inter-atomic distances of Ca-Ca
bonds, Si-O bonds and Ca-O bonds. The MD analysis software, Materials
 101

Studio V 6.1 is used in the present study. For this simulation, the geometry
optimization of the belite molecular structure by using DREIDING force field
is carried out. Based on this study, the molecular structure of all the three
types of -belite are illustrated in Figures 4.21 a, b and c and as such the
mean inter-atomic distances of the bonds of Ca-Ca, Si-O and Ca-O bonds are
calculated and presented in Table 4.10.

Table 4.9 Atomic coordinates of three types of belites

Samples Site Atom x y z

Ca(1) Ca2+ 0.27380 0.34280 0.56940
Ca(2) Ca2+ 0.27980 0.99760 0.29810
Si Si4+ 0.23240 0.78140 0.58170
2-
-C2S (Jost) O(1) O 0.28640 0.01350 0.55990
2-
O(2) O 0.02020 0.74920 0.69190
O(3) O2- 0.48590 0.66820 0.63810
O(4) O2- 0.15580 0.67100 0.42640
BN-Series
Ca(1) Ca2+ 0.20280 0.34350 0.77240
2+
Ca(2) Ca 0.48150 0.99790 0.77970
4+
Si Si 0.15130 0.78060 0.73200
-C2S (Mumme) O(1) O2- 0.22290 0.00770 0.78050
O(2) O2- 0.83300 0.74960 0.52470
2-
O(3) O 0.34610 0.67280 0.98420
2-
O(4) O 0.22870 0.67570 0.65690
Ca(1) Ca2+ 0.27120 0.34420 0.56980
Ca(2) Ca2+ 0.27290 0.99790 0.30010
Si Si4+ 0.23380 0.78110 0.58250
2-
B-series -C2S (Berliner) O(1) O 0.28020 0.01170 0.56020
2-
O(2) O 0.02420 0.74540 0.69020
O(3) O2- 0.48550 0.67370 0.64030
O(4) O2- 0.15920 0.67110 0.42930
 102

Figure 4.21 Molecular structures (unit cell) and calculated inter-atomic

distances of the atoms of (a) -C2S (Jost), (b) -C2S
(Mumme) and (c) -C2S (Berliner)
 103

Table 4.10 Mean interatomic distances of three types of belites

Samples - Mean atomic distances (Å)

Atomic BN-Series B-series
bonds
-C2S -C2S
-C2S (Berliner)
(Jost) (Mumme)
Si O 1.576 1.575 1.614
Ca Ca 3.685 3.458 3.800
Ca O 2.457 2.322 2.597

4.5.2 Fourier Transform-Infra Red (FT-IR) Spectroscopic Studies

The functional group analysis of three synthesized products alone

by FT-IR are presented in Figure 4.22 (a),(b)&(c). In all the methods of
preparation, the belite shows the characteristic bands in the range of
400 - 1200 cm-1 significantly. The bands at 845, 928 and 1010 cm-1 are due to
Si-O stretching and vibration respectively for the silicate polymerization,
which are particularly due to the symmetric stretching vibrations of Si-O-Ca
and Si-O-Si bonds as predicted by Meiszterics et al.(2010) and the
characteristic band at 520 cm-1 also appears due to strong Si-O out-of-plane
bending vibration of silicate. The bands associated with calcite (2920, 2830
and 1405 cm-1) are also present, which may be an impurity or untreated
residual calcite. The absorption band at 3640 cm-1 is due to the O-H bond, and
its intensity reduces considerably in the sintered product spectrum (BN-series
spectrum). The transmittance intensity of the characteristic bands at 521, 845,
928 and 1010 cm-1are very high for BN-series, whereas the same is reduced
significantly in the case of B-series of belites.

These results show that the energy absorption of B-series is very

high to vibrate or dissociate the characteristic bond atoms of calcium silicates
 104

compared to BN-series. Due to this reason, the reaction kinetics of BN-series

is more compared to B-series. Moreover, the size of FT-IR peaks shows the
number of bonds existing in the sample materials. Hence, it is concluded that
the reaction kinetics are higher in the case of BN-series blends than B-series,
because of more energy requirement to dissociate the atoms in the calcium
silicate chain. The characterization studies through XRD, TG-DTA-DTG, FT-
IR and SEM/TEM with EDX confirms the phase transformations occurred
during the processing of the precursors and the formation of -belite by three
synthesis methods as discussed above.

Figure 4.22 FT-IR spectra of -C2S obtained by (a) Hydrothermal

method (b) Mechanochemical method and (c) Solid state
reaction
 105

4.6 SUMMARY

The laboratory experimental studies demonstrated the effectiveness

of thermal analysis of mechanically activated raw materials such as lime
sludge or calcined lime sludge, and nanosilica / silica fume aiming towards
the synthesis of belite phase clinker. The -C2S formed in all the cases is
around 90%; but among all the methods, the solid state reaction method is
highly preferred, since there is no requirement of water and calcination of raw
materials as in other two cases. However, in all three cases towards the
synthesis of -C2S, there is less energy consumption and the synthetic
temperature is much less than the conventional temperature of above 1200°C
without the use of any chemical stabilizers. Hence, this study leads to novel
development of cementitious composite materials for future potential
applications in the construction field. Further, the present study will seek to
hydrate the reactive belite and consolidation in concrete. Hence, the research
and the production of hydraulically active belite-rich cements are very topical
and perspective interest of specialists and environmentalist in the construction
industry. They indicate the possibility of separate industrial production of
special low-energy belite clinker alongside with the production of the
common alite clinker possessing suitable technological properties.

The belite rich cements are suitable for long term sustainable
materials for the infrastructure development and a substitution of a major part
of alite (tri-calcium silicate) to reduce CO2 emission during cement
production can be achieved by belite. Hence, the production of belite cements
attracted the interest of specialists / environmentalists for a long time in the
construction industry. Moreover, several strategies are followed to
compensate for high energy consumption and CO2 emission and making the
concrete more sustainable; one among them is to reduce the alite/belite ratio
of the cement to curtail CO2 emission during cement production. These results
 106

extend the knowledge in the field of heterogeneous reactions in composites

formation. They indicate the possibility of separate industrial production of a
special low-energy active belite clinker alongside with the production of the
common alite clinker with suitable technological properties. Moreover, this
study leads to new routes for developing cement-based composite materials
for future potential applications in the construction field.